Perchlorofluoro alcohols



PERCEORUFLUORO ALCOHQLS Donald W. Wujciak, Union, Robert H. Wade, West Paterson, and William S. Barnhart, Cranford, N. 3., assignors, by mesne assignments, to Minnesota Mining and Manufacturing Company, St. Paul, IVIinm, a corporation of Delaware No Drawing. Application June 24, 1955 Serial No. 517,928

15 Claims. (Cl. 250-633) This invention relates to the preparation of primary, secondary, and tertiary polychlorofluoro alcohols. These alcohols are derived from perchlorofluorocarboxylic acids, preferably having from about 4 to about 20 carhon atoms, or from derivatives of the acids. Suitable derivatives of the acids which may be used as starting States Patent O materials are the acid halides, acid anhydrides, esters,

ketones, and the like. The alcohols may also be derived from perchlorofluoroolefinsj One method for the preparation of the novel polychlorofiuoro alcohols of the invention is by reduction of a perchlorofluorocarboxylic acid, or a derivative thereof. Among the acids which may be reduced are those prepared according to the disclosures of copending applications Serial No. 452,706, filed August 27, 1954; Serial No. 452,704, filed August 27, 1954; Serial No. 452,703, filed August 27, 1954, and Serial No. 452,705, filed August 27, 1954. Derivatives of the acids which may be reduced are acid halides, such as those prepared according to the disclosure of copending application Serial No. 499,250, filed April 4, 1955; esters, prepared according to the disclosure of copending application Serial No. 493,554, filed March 10, 1955; and acid anhydrides and ketones, prepared according to the disclosure of application Serial No. 517,927, filed June 24, 1955.

Generally speaking, this method of preparation consists of the dropwise addition of the reactant, in the presence or absence of a solvent, over a period of from about 15 minutes to about 2 hours, to a reducing agent in an open vessel, with agitation. If ether is used as a solvent, the heat of the exothermic reaction causes the mixture to reflux, hence, temperatures above about 35 C. are avoided so that reduction of a halogen atom is prevented. If other solvents are used, the temperature is controlled at temperatures above 35 C., depending upon the particular solvent used.

After the addition is completed, the mixture is stirred for a period of from about 1 to 15 hours. The reaction mixture is then decomposed by the careful addition of water, ethyl acetate, ether saturated with water, or water-dioxane solution, to decompose any excess reducing agent. The mixture is then poured into an icedilute mineral acid mixture to decompose the salt product. The organic layers are then separated and the aqueous phase is extracted with a solvent such as ether, ethyl acetate, carbon tetrachloride, and the like; The combined organic layers are then washed with a basic solution, such as a mixture of sodium bicarbonate and sodium chloride, until the washings are neutral. The solution is then dried, the ether is evaporated and the product is distilled, if a liquid, or recrystallized, if a solid.

Caution must be observed when using certain reducing agents, such as sodium-alcohol and lithium aluminum hydride. It is essential that the alcohol, preferably ethanol in the case of sodium-alcohol, be perfectly dry in order to avoid hydrolysis. When the lithium com pound is used, the reactor must be dried and flushed with nitrogen before the inorganic compound is added, and the entire reaction and decomposition are conducted in an atmosphere of nitrogen.

Perchlorofiuoroaldehydes, which may be most conveniently prepared by reacting perchlorofluoronitriles, prepared according to the disclosure of copending application Serial No. 509,408, filed May 18, 1955, now Patent No. 2,788,362 with reducing agents such as lithium aluminum hydride and sodium borohydride, may be, in turn, reduced with mixtures of aluminum alkoxides and alcohols. In this method, the perchlorofiuoroaldehyde, aluminum alkoxide, such as aluminum isopropoxide, aluminum t-butoxide, or the like,,and an alcohol are mixed in a reactor. The mixture is heated at a temperature between about 50 and C. to drive oft the carbonyl compound formed, which corresponds to the alcohol used. A suificient reaction time is generally about 24 hours; however, if a large excess of aluminum alkoxide is used, the reaction occurs almost immediately and is completed within about one hour. The solvent and by-products are then removed by distillation'and the residue is hydrolyzed with a dilute base or a mineral acid. The crude product is then extracted with a low-boiling organic solvent, dried, concentrated, and redistilled, if the product is a liquid, or recrystallized, if the product is a solid. 7

Another method for the preparation of the alcohols of the invention is by the reduction of esters of perchlorofluorocarboxylic acids, such as those disclosed in copending application Serial No. 493,554,'filed March 10, 1955, in which a mixture of sodiumand alcohol is used as the reducing agent. A large excess of alcohol and sodium is used in this reaction and the mixed reactants are first cooled in an ice bath until the reaction has subsided, after which the mixture is allowed to warm to room temperature. The reaction mixture is subsequently heated on a steam bath until all of the sodium has reacted. The resulting product is diluted with water, the solvent is distilled, and the crude product is separated by extraction. The extract is washed with Water, dried, and distilled or recrystallized.

The reduction of ketone and ester derivatives of perchlorofiuorocarboxylic acids, as well as the reduction of perchlorofluorocarboxylic acid halides, anhydrides and aldehyde derivatives, may also be effected in a bomb or autoclave under pressure and, in the case of acid halides, this method is preferred. In Table II'below are summarized the operating conditions and catalysts used for each class of compound. All of these catalytic reductions are effected in the presence of hydrogen under pressure, the general procedure being as follows:

To the catalyst and prechlorofluoro or polychlorofluoro acid derivative in an autoclave is added, without agitation, cold hydrogen under pressure. The acid derivative may be reacted in the absence or presence of a solvent; after the addition is completed, the mixture is shaken and heated. Agitation is continued by rocking the auto-' clave during the reaction period until the calculated quantity of hydrogen is taken up, after which the autoclave is cooled and the hydrogen is vented olf. The reaction mixture is then filtered from the catalyst and, if a solvent has been used, it is evaporated 0E. The crude product is distilled, if a liquid, or recrystallized, if a solid.

Perchlorofiuoro or polychlorofluoro compounds which may be reduced in accordance with this invention, the re- 1 ducing agents or catalysts which may be used, and the Patented F eb. 25, 1958 decomposed withabout- 2 nercentfsulfurieacid'brby pouring-the reaction mixture=-ontoiceand g t; 9 PQQFV Q v rconditionszof the reductiqmrea'ctions'are given in Tables 1 V Iand1lbelow': 1 j

i. gees-e97 a acid; In the event me reaction" zu-oductd'ssensiti s h thyd fa ngsaction of mineral acidstitis nbesttoeffecte o TABLEI i 1 t 7 Reduction of polyql zlgrofluoro compounds at atmospheric 7 i The; ketone and; ester: derivatives bf 'perchlorofluorocarboxylic acids, aswell as perchloiofluorocarboxylic acid halides and I anhydrides, may 'also be; reacted with Grig-' nard' reagents to produce tertiary; alcohols. Reaction of t perchlorofluoroaldehydes with Grignard reagents produces secondary alcohols; suitable Grignard reagents 8161211056 having-the formula: j J

n-Me iniwhich R is; fort example 'a methyl, ethyl propyl, allyl,

crotyL'cyclopropyl, cyclobutyl, phenyl orbenzyl radical i and-:X ishalogen;

- Generally speaking, inrtliis: method ofiprenaration the i f gentilnless it is the same. solvent used for the o i ive; It is sometimes 'desirabletousea hlg'lier 60 boiling solventto support higher reaction temperatures used'inthe'subsequent reaction. The mixture 'is tagitated and allowed to reflux, if-alow-boilingsolventis'used, andif'a high-boiling solvent 'is'employed, refluxingis not es- V sentiali The Gr'ignard products obtainedg having the formulaf i H 4 i 1 oM X on xf V V :JRABQ-Rfor 119E4 2) i a vMolarmtioof V 7 V t t a fluoroorr t acidoracid "Reaction o a v l 'olychioroh 2; to iRedncmg-tage'nts .derivvto rednctemp. 0.) Reaction time 7 Solvents n m-. mgagent r pounds'f p 7 V h I '7 li dride sodlum boroh 231' to 1:20; 2:1' to 1 50;, "Immediate 1: 0:48 1 Ethyl'ether ;tetrahydroiuran, qqpa'nqe V V V 1 1:01:10. V 0to80 V hours; lmmedi- "dioxane; 'dibutyl etheij;

I 7 i 1. 1 t o 7 a Iatetgr24hours}: "fiwgltentletch Lithiumaluminumh dridesndiumborohy-t 2110 1:10; 2:1 7-20to150; mme ate to 48 V e ano,e ano e y e er, ,7 7 it dridegisodinm ama lgain,psodinm+alcohoi '7 'to,1;5. Oto 80. 1 hours:immedi-' tetrahydro furan; dloxane, (pr'ei. ethanol). 7 r Q r t ate'to 24 hoursJ' 'water, etc. V Lithiumeldminur'n hydridefsodium borohy- 2:1 to 1:20; 2:1 -20 to 150; 2 to 56 hrs.; 5to Ethyl-ether, 'tetrahydroiuran,

drido} sodiumgnmalgemi,sodium+alcohol to 1:12. 0 to 80. 241x51 V V A dioizzianex d butyl ether, A

h 17. t V L s waer ec. Liiz liiu fi gluminum hydrideflrsodium'boro- 2:1 t011:; 1:1 0 too 30 2231130 l 1rs.;,5 to- Ethyl ether, tetrahydroiuran; V v I to1:5; o V w Ktones; Aluzni r iu n' alkoxidesl-aleohol (isopropanoL 3:1 to 1:10; 1:1 Oto 200; 30 7 Immediate to 72 Methanol, ethanol,- isoproethanol; or anvaleohol'; except: t-alcs.),- t0'1:5. t0150. hours;immedipanol, butanol, aC0t10;3Cld, r 1 7 sodium amalgam; zinctdust, acetic acid. t ate to 24 hours. water, etc. rAldehydesrun Lithium aluminum hydride, sodium borohy- 2:1 to 1:10; 2:1 30 to 200; Immed1ateto-48 Methanol, ethanohethyletliet i l dride,s odium amnlgam aluminum alkoxide i:o1:5 I t0150. hours; immediv V cyclohexanewateneter.

' +alcohol (isopropanoh ethanol, or any 7 i am to 24 l10urs. 7 1

alcohol; ezicepti talcs.) sodlum-j-alcohol I t (ethanoDV 7 v v V t t r I e 7 7 V TABLEII I v Catalytic reduction of pei'chlorofluoro compounds with; r t H -underpressurei I V r 7 h 7 V V l t V V, MoIarratloofperglliggif Catalyst Pressure (p.s,l. g.) Tlmm rsit V tTemp v C; :chlorofluoro comf- Solvents (rarelyused). Mi 7 j I poundtoh'ydrogen to I h' mite Rane 750 to 6000;1500 Immediate r6168 imso toraooym injwmnoyrzs; 'Butyl ether'dioxane 'Agd 2531251 'gietinum pal t mediate 1 24- to 175. to 1:200. alcohols satd hyi t indium, l i i drocarbon' 'hexane Z i 1 I t Im edit i 168 got 300 ltcylcylohexanek r1 nto 6,000,1000 me ae o im.- 0 ;7O ,1: .olzlouynlto o. f 4cm i A m 3,00 magin 12:242.; m 17 5. n25. a t 7 0.500; 5't01O0, name in e 0 0 50; 0 Into 1:50; 1:1t0 1 o t i r f i""f' 7 5t 1 medat: tr; 12 10 4 I 1:15. t 1 7 r 750 we 000; 1,000 mme ia e 0 -o 0 71:1to1: oo;1;1 0 0. Ester? rodeo t g qq'on mediatetoZl to 150; t 1:5OJ r Ket do m;-1,0 00; 250 to Immediate to 24; mi- 30 to 200; 30 1:1 to 1:2Q0; 1.1 to Do. 7. r s

t t v 7 750,1 t medlatet016; 150. "135. V t

hydrolysis with saturated ammonium chloride solution or recrystallized; 1 V y i y Generally-speaking,ftheacid derivatives are reacted in t The solvent is then removed and-the product is distilled the presenceor 'absence 'ofta solvent, such as ethyl ether;

tetrahydrofuran, butyl ether, benzene, toluene, xylei1e,1and the like; :ItlfSQtiSSential thatlthe; Grignard'r'eagentbe solved in a solventoflthis type; Tlienaolarratidofjaeid derivative IO: solvent (if oneisusedfis. between abourttl :2: and about 1:10 while the'molar ratio of. Grignardreagent" to solventis between about 1:2 andaboutj1z50, prefer- 5 ably between aboutlgj' andiabout 1:20; The tempera ture usedin'this reaction may be betweenabout' Oto 7 Ci; oras high as the "reflux teinperature ot-th'e-solvent; e; V 7

142. C, is the boiling point *ofdibutyl ether? The term perature is 'preferabIy in the range 'of-about 30'"; C. to'flie' V reflu x temperature of the solvent; used; The "product be;

gins t'o'fo'rm; immediately-mud :the reaction mav-be ex-l' tended over afiperio'd of 24 hours, 1 although it is 'usually-i complete within aboutfi fhoui si' The-molar'ratio ofi'acidi derivative to Grignardreagentu'sedin this' reaet ion'varies r between about l:1'and about'l'zl0, and is preferably between about :151 and about 134; i

- The novel polychlorofluoro' alcoholsjof -the invention may alsobe prepared"byfree radical catalysis from a f terminally unsaturated perchlorofluoroolefin, prepaiedflao cording to the disclosure' of-copending applicationgs erial alcohol thereto. This method consists of reactin unsaturated perchlorofluoroolefin in a molar ratio of alcohol to olefin between about 1:1 and about 10:1, preferably between about 2:1 and about 6:1, in the presence of a catalyst.

Suitable catalysts for this reaction include peroxide catalysts such as benzoyl peroxide, acetyl peroxide, t-butyl hydroperoxide, t-butyl perbenzoate, and the like, and of these, benzoyl peroxide is preferred. The catalyst is used in an amount varying between about 0.5 and about 1.0 percent by weight of the reactants. The reaction temperature may be between about 80 and about 200 (3., preferably between about 100 and 130 C., and the reaction time may be between about 1 and about 48 hours, preferably from about 2 to about 16 hours.

The novel polychlorofiuoro alcohols prepared by the method of this invention are useful as solvents, surfactants, disinfectants, fungicides, chemical intermediates in the preparation of other highly halogenated derivatives and as primers for polychlorotrifiuoroethylene plastic coatings.

The preferred polychlorofluoro primary mono alcohols of this invention have the formula,

in which Z is chlorine, or a perhalomethyl radical having a total atomic weight not in excess of 146.5, and n is an integer from 2 to 10.

The preferred polychlorofluoro secondary mono alcohols of this invention have the formula,

in which Z and n are as given above and R is an alkyl, aryl, alkenyl, cycloalkyl, cycloalkenyl or heterocyclic radical having not in excess of about 20 carbon atoms.

The preferred polychlorofluoro tertiary mono alcohols 01" this invention are those having the formula,

in which Z and n are as given above and R and R are alkyl, aryl, alkenyl, cycloalkyl, cycloalkenyl or heterocyclic radicals having not in excess of about 20 carbon atoms.

Exemplary of the unsubstituted alkyl radicals which may be used in the above formulas are methyl, ethyl, propyl, butyl, and the like and isomers thereof, while substituted aryl radicals may be 2-ethoxyethyl, Z-methoxyethyl, and the like and isomers thereof; unsubstituted aryl radicals may be phenyl, xylyl, ethylphenyl, cymyl, duryl, cumyl, naphthyl, methylnaphthyl, benzyl, and the like and isomers thereof, while substituted aryl radicals may be anisyl, dimethoxyphenylene, chlorophenyl, chloroxylyl, dichlorophenylene, chloroanisyl, chloronaphthyl, dimethylaminophenyl, vinylphenyl, cresyl, hydroxyphenyl, aminophenyl, and the like and isomers thereof; unsubstituted alkenyl radicals may be allyl, butenyl, pentenyl, and the like and isomers thereof, while substituted alkenyl radicals may be 2-ethoxyallyl and the like; unsubstituted cycloalkyl radicals may be cyclohexyl, cyclopentyl, cyclobutyl, bornyl, methylcyclohexyl, camphanyl, and the like and isomers thereof, while substituted cycloalkyl radicals may be methoxycyclohexyl, dimethylaminocyclohexyl, and the like and isomers thereof; unsubstituted cycloalkenyl radicals may be cyclohexenyl, cyclopentenyl, methylcyclohexenyl, and the like and isomers thereof, While substituted cycloalkenyl radicals may be methoxycyclohexenyl, and the like and isomers thereof; and unsubstituted heterocyclic radicals may be pyranyl, fury], pyrryl, thienyl, pyridyl, pyrazinyl, and the like and isomers thereof,-while-substituted heterocyclic radicals may be chlorofuryl, chloropyrryl, chlorothienyl, dichloropyrtyLmethoxypyridyl, and the like and isomers thereof.

Diols having an even or odd number of carbon atoms may also be prepared according to the invention, the diols having an even number of carbon atoms having the formula,

in which n is an integer from 2 to 9.

The mono and dialcohols prepared by the addition of alcohols to perchlorofluoroolefins are slightly different in structural configuration, compounds having the formula,

in which Z is as given above, 71 is an integer from 2 to 9, and y is an integer from 1 to 3, being exemplary of the mono alcohols produced by this method; and compounds having the formula,

in which n is an integer from 1 to 7, and y is an integer from 1 to 3, being exemplary of the diols produced by this method.

The invention will be further illustrated by reference to the following specific examples:

EXALIPLE 1 Preparation of Cl(CF CFCl) CF CH OH.-In a 2 liter S-necked flask fitted with a nitrogen inlet, stirrer, condenser and dropping funnel were placed 420 ml. of ether containing about 0.4 mole of LiAlH Then a solution of 100 grams (0.2 mole) of Cl(CF CFCl) CF COCl in 150 ml. of ether was added gradually over a 2 hour period with stirring (under nitrogen). The etherrefluxed, due to the heat of reaction. After stirring the mixture (ether and LiAli-L, complex) for an additional hour, the excess reagent and the complex were decomposed by the careful addition of 60 ml. of water with vigorous stirring. The mixture was poured into 1.3 liters of 10 percent H 80 to dissolve the insoluble hydroxides. The ether layer was separated, the aqueous layer was saturated with anhydrous Na SO (300 grams), and extracted three times with ether. The combined ether layers were washed with a saturated NaCl solution, 5 percent NaHCO solution, again with a saturated NaCl solution and were finally treated with anhydrous calcium sulfate. The ether was evaporated and the liquid residue distilled through a 6 inch Vigreux column. The followmg fractions were collected:

Cl anal. No. Gms. B. P. (14 am 11. MRn

mm), C

Calcd. Found 2. 4 117-118 1. 719 1. 3650 60. 5 30. 4 11. 9 10.2 118-122 1. 741 1. 3659 59. 9 14. a 122-138 1. 802 1. 3333 21. s 133-141 1. 847 1.3961 60. s 18. 4 141-141. 5 1. 863 1. 3982 so. 4 a0. 4 30. 2 9. 9 141. 5 1. 862 1. 4003 60. 7 2. 2 141. 5 1. 855 1. 4004 60. 9 -1 2.0 Residue 1 Calculated 60.79.

It was believed that fractions 1 and 2 were the aldehyde, but spectral analysis revealed strong alcohol and weak carbonyl absorption. Fraction 5 showed only a strong alcohol absorption. Dehalogenation obviously occurred in fraction 1.

7- was prepared in ether by th reaction. of magnesium and methyl iodide; Tether solution of 5 (0.45 molel-was added under an atmosphere of nitrogen at a rate suflicient'to maintain a moderate reflux. After standing overnight, the solution was decomposed with saturated NH Cl and the precipitated solid was contain hydroxyl groups but nocarbonyl band.

' 7 EXAMPLE 3 Additionio f methz mbl to 4,6,7-trichlorctaflu0ro heptene-L-A mixture of 2 moles of methanol and 1.5 grams of beuzoyl peroxide is charged to an autoclave. The autoclave .is cooled with liquid air, evacuated and 0.4 mole of 4,6,7 trichlorooctafluoroheptene-1- is introduced. Theautoclave is then closed'and the contents agitatedv atv 100-1 30 C. for hours. .The unreacted olefin is bled from the autoclave at room temperature and gen). 7

cess'. reagent and the LiAlH complex aredecomposed by I nxntirmt a.

3-necked flask fitted with a nitrogen inlet, stirrer, condenser and dropping'funnel is placed 800 mLof ether, V V containing about-0.8 mole of-LiAlll Asolution-of 0.2 mole of ClC0 (CF CFC1) COCl in,150fml.-'of ether is added gradually to' the flask with stirring .(undennitro The mixture refluxes and after an hour the exthe careful addition of water (100 ml.) with vigorous stirring. The mixture is .then poured into 2.5 liters of rated NH Cl andthe'precipitated solid is extracted -sev-.

undecomposed peroxide is destroyed by the addition of 7 ferrous sulfate or sodium bisulfite to the reaction mixture.. Fractionation of the reaction mixture gives about a EXAMPLE4 Preparation of T071 mole of cu cr cncn cn cu is added'O.25 mole oi LiAli-I in 500 ml. of ether With stirring, and cooling to temperatures as low as 70 C. After the addition is completed, the mixture is carefully allowed to warm to room temperature. The mixture is then decomposed with cold. dilute II-ICl and the product is extracted withether, washed and dried. 3,5,7,8 tetrachloroundecafluorocaproaldehyde is obtained in about 55 percent yield.

' EXAMPLE 5 tion of 0.62 mole LiAIH; m1 liter of ether, is added with.

stirring, 0.5 mole of Cl(CF CECl) CF COOH in 1 liter of ether. During the addition the mixture is allowed to reflux- After the addition is completed, the mixture is refluxed for at least 6 hours-and then cooled. Water (100 ml.) followed by aicold solution of dilute H 50 5 7 .(1 liter) is added to the mixture. The ether layer, is sepa rated, washed with dilute acid, aqueous sodium bicarbonate and then with. water. The solution is then dried and concentrated. The product isdistilled to obtain a yield of about. 50 percent of 3,5,7,8-tetrachloro-1,l-dihydroundecafiuorooctanol. N a

10 percent H to. dissolve insoluble hydroxides. The

ether layerris separatedjtheaqueous layer is saturated with anhydrous Na SO and extracted several times with ether. The combined ether layers are washed with a saturated solution of NaCl, with 5 percentfNaHCO and again with saturated NaCl and are finally drie d over .an-

The ether is evaporated and hydrous calcium sulfate. the liquidis distilled to obtain a yield. of about 50 PEI". cent of 3,5,7 trichloro 1,1,8,8j tetrahydrononafiuoro octa-l,8-diol.

EXAMPLE 7. PREPARATIou on AN ALconoL FROM A KETONE AND A GRIGNARD. REAGENT WHEREIN RISANAROMATIC GROUP Preparation of I our; 1 01(CF3CFC1MCFiC-CIHI J 1 A solution of phenyl magnesium bromide (1.2 moles) is prepared in ether by the reaction of magnesium with phenyl bromide. An ether solution of c1 cr crcil c-P 000 11 (0.4 mole) is added under an atmosphere of nitrogen at a V a rate sufficient to maintain moderate reflux. After standing 16 hours, the solution is hydrolyzed with satueral times with ether. The combined organic solution is concentrated and distilled to obtainja percent of the desired product. 7 EXAMPLE 8.PREPARATION OF AN ALCOHOL FROM ALDEHYDE AND GRIGNARD REAGENT WHEREIN V R 1s A CYCLOALKENE GROUP Preparation of i V V 5 n CltCF10FC1)aCFa-CHCH:QH2CH=CH V H V A solution of cyclopentene magnesium chloride" (0A a mole) is prepared in ether by the reaction between mag nesium and 3-chlorocyclopentene. An ether solution of 0 CHO F40 FGDaCFaC (0.3 mole) is addedunder anatmosphere, of nitrogen at. a' rate suflicient tomaintain a moderate reflux: After standing 10 hours, the solution .is hydrolyiedawith satu rated NH Cl and the precipitated. solid is extracted sevi The combined organiesolution is yield of aboutiooi era'l. times with ether. 7 concentrated and distilled to obtain Ia percentof the desired product- EXAMPLE 9.+PRE2ARAT10N or ALCOHOL .rnon.

V ALDEHYDE AND omen-nan REAGENT wHE ISA HETEROCYCLIC RADICAL .5 B I R I Preparation of. f

. cltorier c1)ieric+.qnecn n=dn+cn=en E;

AT w re d ma ed e yield of about 5 0 V mole) is prepared in ether by the reaction between magnesium and B-bromopyridine. An ether solution of p CROF CFCDgCFaC (0.3 mole) is added under an atmosphere of nitrogen at a rate suflicient to maintain reflux. After standing overnight, the solution is hydrolyzed with saturated NH Cl and a precipiated solid is extracted several times with ether. The combined organic solution is concentrated and distilled.

i 01(CFgCFCDzGF2CCH=CHN=CHCH=CH is obtained in about 50 percent yield.

EXAMPLE 10.PREPARATION OF AN ALCOHOL FROM AN ALDEHYDE AND A GRIGNARD REAGENT \VHERE- IN R IS A CYCLIC BYDROCARBON GROUP Preparation of C1(C F20 F CD30 FzC-(CH-CHy-CHg-CHz-CHg-GHz):

A solution of cyclohexyl magnesium bromide (1.2 moles) is prepared in ether by the reaction between magnesium and bromocyclohexane. An ether solution of (0.3 mole) is added under an atmosphere of nitrogen at a rate suthcient to maintain reflux. After standing overnight, the solution is hydrolyzed with saturated NH CI and the precipitated solid is extracted several times with benzene. The combined organic solution is concentrated and distilled to obtain a yield of about 60 percent of the desired product.

EXAMPLE 11.PREPARATION OF AN ALCOHOL FROM AN ESTER AND A GRIGNARD REAGENT WHEREIN R IS AN ALKENli RADICAL Preparation of C1(O FzC F Cl) C FzC-(CHzCH=CH2)a A solution of allylmagnesiumchloride (0.7 mole) is prepared in ether by the reaction between magnesium and allychloride. An ether solution of FLUOROCARBOXYLIC ACID AND A REDUCING AGENT IN A BOMB Preparation of H 0 013(0 FzC F CD20 Fi l-CH:

One mole of CCl (CF CFCl) CF COCH and 3 grams (0.05 mole) of Raney nickel is introduced into a bomb. Hydrogen is piped in under about 1,000 pounds pressure. The bomb is rocked and heated to 100 C. until the calculated amount of hydrogen is taken up. The bomb is then cooled and excess hydrogen is vented off. The contents of the bomb are filtered and the bomb is washed out with ethyl alchol. The filtrates are concentrated and fractionated to obtain a yield of about 70 percent of the desired product.

EXAMPLE 13.PREPARA'IION OF AN ALCOHOL FROM AN ALDEHYDE USING AN ALUMINUM ALKOXIDEH- ALCOHOL REDUCING AGENT Into a 2 liter 2-necked flask immersed in an oil bath are placed 1 mole of 0 Y 01 0 F20 F CDzC no 600 ml. of anhydrous isopropyl alcohol and 1 mole of aluminum isopropoxide. A fractionating column and a nitrogen tube are attached to the flask. The oil bath is then heated to C. and a slow current of nitrogen gas is admitted. The mixture is allowed to boil vigorously until no more carbonyl compound (corresponding to the alcohol) is distilled (about 24 hrs.). The temperature of the bath is allowed to fall to 120 C. and the alcohol is distilled. When the residue (the aluminum complex) is nearly dry, tie flask is removed from the oil bath and the solid is treated with 250 ml. of 20 percent H 50 and stirred thoroughly to insure complete decomposition. The mixture is steam distilled and the resulting two layers are separated. The aqueous layer is saturated with sodium sulfate and extracted with'ether. This ether solution is added to the main portion of the alcohol which has been distilled and the whole is dried over anhydrous sodium sulfate. The ether is evaporated oil and the crude product is distilled to obtain a yield of about 80 percent of EXAMPLE 14.PREPARATION OF AN ALCOHOL FROM AN ESTER USING SODIUlWI-l-ALCOHOL AS A REDUC ING AGENT A 3-necked round bottom flask is fitted with a stirrer,

a reflux condenser and an opening through which are introduced 3 moles of sodium and 200 ml. of dry toluene.

The flask is heated in an oil bath until the sodium is melted. The mixture is allowed to cool to 60 C. whilestirring constantly. To the mixture is then added 0.5 mole of Cl(CF CFCl) CF COOC l-I in ml. of absolute ethanol. After this addition is complete, 500 additional ml. of ethanol are added rapidly. When the reaction has subsided, the flask is heated on the steam bath until the sodium is dissolved. The mixture is then steam distilled to remove toluene, ethanol, and product. The mixture is then fractionated to remove ethanol. The layers are separated and the water layer is extracted with ether. The organic layers are combined, washed with water, sodium carbonate solution, and again with water and dried over anhydrous magnesium sulfate. The soivents are evaporated and the crude alcohol is distilled under diminished pressure to obtain a yield of about 60 percent of H C1(CFgCFO1)4CH2(!j-H It will be obvious to those skilled in the art that many modifications may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications.

We claim:

1. An alcohol having a perfluorochlorocarbon chain having the recurring unit, -CF CFCl, said chain being bonded at one terminus by a radical selected from the group consisting of a chlorine atom, a perhalomethyl radical having an atomic weight not in excess of 146.5, a --CF CFHCF divalent radical, a --CF CFH- divalent radical, a CFC1 divalent radical, a --CFHCFC1 divalent radical and a CF divalent radical, said perfluorochlorocarbon chain being bonded V atrits. other terminus onlybynne of said divalent radicals,

and in which each of said divalent radicals is additionally bonded to a hydroxyl-containing group selected from the' ccnsi stin toru wherein y is an integer from 1 to 3, and R and R are selected from the group consisting of alkyl, aryl, alkenyl, cycloalkyl, cycloalkenyl and heterocyclic radicals having not in excess of 2.0 carbon atoms per radical. V

2. 'An alcohol having theformula,

Z'(CF CFCl) CF CH OH in which Z is selected from the group consisting of V A chlorine and perha'lomethyl radicalshaving' a total atomic weight not in excess of 1465, and a to 10. r

n is anzint'eger from 2" a 3. An alcohol having the formula,

Cl(CF -CFCl), CF CH OH in which n is an integer from 2 to 10. 4. An alcohol having the formula,

V 7 H Z(-Q.Fg-CECl)e-1OF:(3R

V in whichZ'isselected frornthe group consisting :of chlorine and perhalomethyl radicals having a total atomic weight not'in excess of 146:5,12 is an integer from 2 to 10, and R is selected from the group consisting of alkyl, aryl alkenyl, cycloalkyl, cycloalkenyl and heterocyclic radicals having not in excess of about 20 carbon atoms;

5. An alcohol having the formula,

V V V 3 C1(C 2 CFCl)n*lCF:?-R

in which n is an integer from 2' to 10,v and Risselected from the group consisting of alkyl, aryl, alkenyl, cycloalkyl, 'cycloalkenyl and heterocyclic radicals having not in excess of about 20 carbon atoms. 7

6. An alcohol having thejformula,

7 in which 2 is selected from: the group consisting of chlorine and perhalomethyl radicals having a total atomic weight not in excess of 146.5, n is an integer from 2 to 10, and'R and R are selected from the group consisting of alkyl, aryl, alkenyl, cycloalkyl, cycloalkenyl, and

eese.

heteroeyclic radicals having not in excess of about "20'.

7 carbonratoms. a c

I notnscn' n mtcn 7. A' dial having "the formula, I V I HQH C-CFCl(CF CFC1) ,EQCF CH OH in which n is an integer from 2 to 9. V

8. A diol having the formula, V V

H non qcF -r-cFcb cF cn on in'whi'chn is'an integer from 1 to 8.

'9. Anialcohol having the formula,

z c1'=, c1=*ci ,,;,c1= c1=Hc1= cnn on in which Z is selected from the group consisting of chlorine and perhalomethyl radicals having a total atomic weight '7 not in excess 0351 165, 12 is an integer from 2 to '9, and

y is an integer from -1 to -3.-

10. An alcohol having the formula,

in which in an .integer'-fro1n i 27 to 9, andy is an integer from 1 to 3.

11. A diol having theformula,

cucncFcn cncn on 1'4. An-alcohol having the formula, V

a V V alkyl radicals having not in excess of about 20 carbon atoms 7 I V a I 15. An alcohol hav'ing the formula,

, g o1 -cm-oromo Ego-0H1 7 CH3 7 References Cited in the-file of this patent 'UNITED STATES PATENTS 2,559,628 Joyce July 10, 1951 2 ,6 6,?797 Husted et a1. V 'V Jan. 1179, 1954 from to 7 and y is'an integer UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,824,897 February 25, 1958 Donald W. Wujciak et al.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 8, lines 71 to 74:, and column 9, lines 13 to 16, the formula in each occurrence should appear as shown below instead of as in the patent n C1(OF=CFCDQCFz3--C=CHN=CHCH=CH Signed and sealed this 12th day of August 1958.

Attest KARL H. AXLINE,

Gammissoner of Patents. 

1. AN ALCOHOL HAVING A PERFLUOROCHLOROCARBON CHAIN HAVING THE RECURRING UNIT, -CF2CFCI-, SAID CHAIN BEING BONDED AT ONE TERMINUS BY A RADICAL SELECTED FROM THE GROUP CONSISTING OF A CHLORINE ATOM, A PERHALOMETHYL RADICAL HAVING AN ATOMIC WEIGHT NOT IN EXCESS OF 146.5, A -CF2CFHCF2- DIVALENT RADICAL, A -CF2CFH- DIVALENT RADICAL, A -CFCI- DIVALENT RADICAL, A -CFHCFCI- DIVALENT RADICAL AND A -CF2-DIVALENT RADICAL, SAID PERFLUOROCHLOROCARBON CHAIN BEING BONDED AT ITS OTHER TERMINUS ONLY BY ONE OF SAID DIVALENT RADICALS AND IN WHICH EACH OF SAID DIVALENT RADICALS IS ADDITIONALLY BONDED TO A HYDROXYL-CONTAINING GROUP SELECTED FROM THE GROUP OF CONSISTING OF 